Detergent composition



Patented Jan. 21, 1947,

2,414,452 7 DETERGENT COMPOSITION Joseph Cunder, Newark, N. J., assignor to National Oil Products Company, Harrison, N. J., a corporation of New Jersey No Drawing. Application July 1, 1943,

Serial No. 493,107

This invention relates to nonirritating detergent compositions for use in contact with the skin, and particularly to such compositions containing sulfated fatty materials.

A" wide variety of materials have been proposed hitherto as detergents for use in contact with the skin. Generally, such compositions have sought simultaneously to meet two requirements (1) mild action on the skin and (2) effective detergent action in any and all waters of varying hardness and salt content. A particularly urgent need exists for an effective but mild salt water detergent, whereby naval personnel may wash their persons, their clothes and the equipment of their vessels with sea water without deleterious elfects upon their skin. Salt water" soaps for this purpose have hitherto been prepared from coconut oil, but such soaps have been found to be notoriously hard upon the skin.

Moreover, aside from the problem of providing ef-,

fectlve salt andhard water detergents, even the so-called "mild" soaps, such as castile soap, leave much to be desired in the mildness of their action on the skin.

Accordingly, it is an object of this invention to provide a detergent composition having no deleterious effect upon the skin of the user, but which will nevertheless exert a highly efi'ective detergent effect in hard water and in saline waters such as sea water.

Another object is to provide such a detergent composition which will have an even milder action upon the skin than the-hitherto accepted mild'soaps such as castile soap.

Still another object is to provide such a ,composition which may be made from readily and cheaply procurable starting materials.

The foregoing and other objects may be achieved in accordance with this invention in compositions containing sulfated. fatty materials together with alkali soaps, the acyl radicles of which contain at least 16 carbon atoms, soaps of any shorter-chain fatty acids and of unsaturated acids of any chain length being excluded so far as is practical. The resultant compositions, notwithstanding the relatively poor detergent and foaming capabilities of their several ingredients, exert powerful detergent and lathering' efi'ects in hard water and in saline waters such as sea water. Despite these excellent and eifective prop- 8 Claims. (01. 252-121) erties, the products of this invention exert no deleterious effects upon the skin of the user, be-

ing in fact superior in this respect to the soaps hitherto considered the mildest possible, such as the oleate soaps on the order of castile soap.

Sulfated fatty materials suitable for incorporation into the detergent compositions of this invention include any of the sulfated animal, fish or vegetable fatty oils, fats or waxes. such as sulfated castor, corn, cod, cottonseed, menhaden, mustardseed, neat's-foot, olive, peanut, rape, rice bran, safliower, seal, sesame, soyabean, sperm, teaseed, whale, and like oils. Likewise, the sulfated fatty acids may be employed, such as sulfated oleic acid, or the sulfation products of mixed fatty acids derived from the oils, fats and waxes above named. Fatty materials of varying degrees of sulfation may be employed; however,

it is highly preferred to employ sulfated oils containing rather high percentages of S03, preferably in excess of 13% S03 based on the dry weight of the oil.

Suitable soaps for incorporation into the de tergent compositions of this invention should be constituted, as nearly as is practical, entirely of fatty alkali soaps, the acyl radicles of which are saturated and contain at least 16 carbon atoms. Sources of fatty materials for the production of suitable soaps will be obvious to those skilled in the art. For instance stearic acid, derivable by the fractional crystallization of fatty acids derived from the splitting of fats, affords an economical source for the fatty components of the soaps employed in the compositions of this invention. Also, the natural fats, oils and waxes and fatty acid mixtures containing both satu rated and unsaturated fatty acyl radicles principally of fatty acids containing 16 or more carbon atoms may be hydrogenated to convert the unsaturated fatty radicles to saturated radicles to provide suitable fatty components for the soaps employed in this invention. Oils which may be rendered suitable for use in this invention by hydrogenation are practically any of the fats of the large land animals, such as beef tallow, mutton tallow, lard, lard oil, horse fat and the like; also practically any of the marine oils such as cod .oil, menhaden oil, pilchard oil, whale oil, seal oil. and the like; and also many of the vegetable oils such as palm oil (fruit coat, as dis a anus:

tin uished from seed), olive oil. hempseed'oil, grapeseed oil, teaseed oil, saiilower oil. sunflower oil: castor oil, pumpkin seed oil, rice oil, mustard oil, rape oil, soyabean oil and the like. The amounts of the various fatty acids in the commercial oils and fats, and therefore their suitabilities for use in this invention, are well known,

see Hilditch The Chemical Constitution of the one method, the alkali soap of fatty acids containing 16 or more carbon atoms may be manu- 4 firmed by patch tests tabulated at the end of Example IV hereinbelow.

Example 11 Parts Highly sulfated oleic acid- (moisture 38%,

80: 15.5% on dry weight of oil) Sodium soap (anhydrous, powdered, from hydrogenated tallow having an iodine value 48 of 5) The listed ingredients were heated together with stirring at 95 0.. until a homogeneous melt was secured, after which the melt was slowly cooled to room temperature. The resultant product was a firm, solid cake having the same excellent detergent properties and mild action on factured separately and then incorporated with I the sulfated fatty material by heating and stir-. ring. For this purpose, the powdered and granular anhydrous soaps produced by the lately developed continuous soap-making processes are quite convenient. Alternatively, the soap may be generated in the final mixture by simultaneously'mixing and heating a sulfated fatty material, a saponifiable fatty material capable of yielding soaps suitable for incorporation into the compositions of this invention. and an alkali.

The products of this invention may have incorporated therein various fillers, detergents, wetting agents, abrasives and the like. For instance, moderate amounts of rosin soaps may be incorporated therein, without substantially detracting from the excellent properties thereof. Examples of suitable abrasives are pumice, infusorial earth, and the like.

With the foregoing general discussion in mind, there are given herewith detailed specific examples of the preparation of detergent compositions according to this invention. All parts given are by weight.

Example I Parts Highly sulfated oleic acid (moisture 38% on total oil, 803 15.5% on dry weight 0! 011)-- 54 Caustic soda (50% aqueous)- 8 Sodium resinate (anhydrous, powdered) 4 Sodium soap (anhydrous, powdered, from hydrogenated sardine oil having an iodine value of 8) 36 The sulfated oleic acid and soda were mixed at room temperature and the mixture heated to 85 C. While maintaining this temperature, and with continued agitation, the sodium resinate and sodium soap were added. Thereafter the mixture was allowed to cool and formed a uniform, firm, solid cake. suitable as a cake detergent for use in contact with the skin, as it lathered freely and exerted a highly effective detergent action in removing the usual soils from the skin. and from fabrics and massive solid substrates, even when used in extremely hard water and sea water. The material. notwithstanding its detergent eiliciency. was found in actual practice to have no adverse eflect upon the human skin, which finding was con- This material was found to be highly.

the human skin characterizing the product of Example I. Patch tests conducted upon this material are tabulated following Example IV.

Example III Parts stearic acid (commercial, triple pressed) 88 Caustic soda (30 B.) Sulfate-d oleic acid (moisture 38%, 15.5%

on dry weight of oil) '58 Water 180 like detergent. Patch tests conducted upon the material are tabulated after Example IV.

Example IV Sulfated oleic acid (moisture 30%. S03 9% on dry weight of oil). 50 Caustic soda (50% aqueous) 25 Rosin 15 Hydrogenated castor oil (iodine value 5)---- 10 The hydrogenated castor oil, rosin and caustic soda were heated and stirred together at 90 C. for two hours. Thereafter the temperature was raised to boiling until the loss oi water rendered the mass highly viscous. Thereafter the sulfated oil was added and stirred into the mass, which was then cooled. The resultant product had the same excellent properties characterizing the products of the preceding examples.

In order to confirm the conclusion, drawn from practical experience and tests, that the detergent compositions of this invention exert noharmiul action upon the skin. patch tests were run upon the everal produets'produced as described above and also, for purposes of comparison, upon pure sodium soaps of individual fatty acids. These tests were carried out by application of a 1 inch square patch of surgical gauze saturated with a 15% aqueous solution of the soap in question to the skin of a human subject for 24 hours. A

given test was taken to have a positive result when markederythema or any more drastic response occurred. The results of these tests are tabulated herewith.

No. of No. of Material under test positive negative reactions reactions Product of Example I 0 100 Product of Example II... 0 100 Product of Example III..- 0 100 Product of Example IV-.- 0 100 Sodium laurato 52 38 Sodium myristatc 11 89 Sodium oleate..' 19 81 From the foregoing table, it will be seen that the products of this invention are vastly milder in their action upon the skin than sodium laurate and myristate, which typify salt water soaps, the only soaps hitherto produced which have the capability of foaming and exerting detergent action in sea water. and hard water. The products have nevertheless been found to possess all the procurable sulfated fatty materials and hydro- .genated oil.

What is considered to be novel and desired to be secured by Letters Patent is: g 1. A mild, nonirritating skin cleansing composition comprising sulfated oleic acid and an alkali metal soap of a saturated fatty acid containing at least 16 carbon atoms, said composition being substantially devoid of soaps of unsaturated fatty acids, soaps of fatty acids containing less than 16 carbon atoms, organic solvents and other skin irritating factors;

2. A mild, nonir'ritating skin cleansing composition comprising sulfated oleic acid and analkali metal stearate, said composition being substantially devoid of soaps of unsaturated fatty acids, soaps of fatty acids containing less than 16 carbon atoms, organic solvents and other skin irritating factors.

3. A mild, nonirritating skin' cleansing composition comprising sulfated oleic acid containcapabilities of salt water soaps in the regards cited. It will also be seen that theseproducts,

notwithstanding their vigorous foaming and de-' tergent properties, are in fact milder than sodium oleate, which typifies the true castile soaps, hitherto regarded as the mildest soaps available.

Sodium resinate Sodium soap (anhydrous, powdered, from completely hydrogenated soyabean oil) 36 The ingredients listed in each of the Formulae 1 and 2 were compounded together exactly as were the corresponding ingredients in Example I. The resultantproducts formed firm cakes, and exhibited the same ready solubility, foaming,

and the effective detergent action in ordinary and sea water characteristic of the other products of this invention. The products of this example were found in practice to have a very mild action on the skin.

From the foregoing general discussion and detailed specific examples, it will be seen that this invention provides novel detergents which are highly effective in all waters, both fresh and salt.

Notwithstanding their excellent properties, the products of this invention are very mild in their action on the human skin; 'Ihe products are, moreover, very simply produced from the readily ing in excess of 13% S03, based on the dry weight of the oleic acid, and an alkali metal soap of a saturated fatty acid containing at least 16 carbon atoms, said composition being substantially devoid of soaps of unsaturated fatty acids, soaps of fatty acids containing less than 16 carbon atoms, organic solvents and other skin irritating factors.

4. A mild, nonirritating skin cleansing com position comprising sulfated oleic acid containingin excess of 13% S03, based on the dryweight of the oleic acid, and an alkali metal stearate,

said composition being substantially devoid of soaps of unsaturated fatty acids, soaps of fatty acids containing less than 16 carbon atoms, organic solvents and other skin irritatingfactors.

5. A mild, nonirritating skin cleansing composition comprising sulfated oleic acidand a sodium soap of a saturated fatty acidcontaining'at least 16 carbon atoms, said composition being substantially devoid of soaps of unsaturated fatty acids, soaps of fatty acids containing less than 16 carbon atoms, organic solvents and other skin irritating factors. I

6. A mild, nonirritating skin cleansing composition. comprising sulfated oleic acidand sodium stearate, said composition being substantially devoid of scans of unsaturated fatty acids, scans of fatty acids containing less than 16 carbon atoms, organic solventsand other skin irritating factors.

7. A mild, nonirritating skin cleansing com .position comprising sulfated oleic acid containing in excess of 13% S03, based on the dry weight of the oleic acid, and a sodium soap of'a saturated fatty acid containing at least 16 carbon atoms,

said composition being substantially devoid 'of soaps of unsaturated fatty acids, soaps of fatty acids containing less than 16 carbon atoms, organic solvents and other skin irritatingfactors.

8. A mild, nonirritating skin cleansing'composition comprising sulfated oleic acid containing in excess of. 13% S03, based on the dry weight of the oleic acid, and sodium stearate, said composition being substantially devoid of soaps of unsaturated fatty acids. soaps of fatty acids containing less than 16 carbon atoms, organic solvents and other skin irritating factors. f p

JOSEPH connaa. 

